Treatment of hydrocarbon oils



i moved; such a treatment being particularly adaptwhere relatively heavy treatments are desired. 110

Patented Feb. 6, 1934 1,946,095

TREATMENT OF HYDROCAR BON' OILS Jacque C. Morrell and Gustav Eglofi, Chicago,

Ill., assignors to Universal Oil Products Company, Chicago, 111., a corporation of South Dakota No Drawing. Application February 16, 1931 Serial No. 516,277

4 Claims. (01. 19636) This invention relates to the treatment of ed to the refining of vapor phase or high temperahydrocarbon oils, and refers more particularly ture cracked distillates. to the refining of relatively low boiling hydro- In some cases the contact masses may be mixed carbon distillates at elevated temperatures, eswith minor'amounts of materials of a basic na- 5 pecially those resulting from the conversion of ture,-such as metals or their oxides, these resultrelatively high" boiling hydrocarbons at elevated ing in'some instances fromthe decomposition temperatures- 3 of salts of the metals incorporated with the More specifically the invention comprises subearthy materials prior to their roasting and in jecting hydrocarbon oil vapors to treatment with other instances from the disintegration reactions 10 the acids of phosphorus in the presence of solid of the earthy materials during their use in the contact materials of a non-metallic nature, such process. The effect of the bases may be of a as fullers earth, clays, bentonite, bauxite, crushed chemical or merely of a catalytic-mature. fire-brick, pumice stone and other materials of The invention is more particularly directed to an earthy or siliceous nature. Oxygen-containthe treatment of vapors of lower boiling cracked l5 ing gases, such as air, oxygen, ozone alone or in distillates, though straight run distillates may combination, may also be employed in the treatalso be treated within the scopef of the invention; ment, ozonized air having been found to be par- In applying the process of the invention to ticularly efiicacious in some instances. practice any suitable equipment maybe em- Owing to its varying valence, phosphorus forms ployed which will permit contacting the mixture 20 an extended series of acids which correspond to of hydrocarbon vapors, oxidizing gases and steam the different oxides mixed with various molecular with the liquid or solid acids and the solid conequivalents of water. The following table will tacting or polymerizing materials; for example, a give briefly the commoner acids of phosphorus: suitable tower or chamber packed with a selected mixture of contacting materials may be employed 25 HPo, (Floss H10) orthophosphorwi Q; deal following the fractionator of a cracking system,

200 0. the oxidizing gases and steam being introduced Hymphwpmmusggf when used at a suitable point,;or points along Elmo, Pzo..2H,o Hypophosphoric.. M7. F. 55 0.; dec. the line of flow of the ascending or descending O .2110 h s o vapors. Similarly, any device which permits the :5; 5 S3 39 33 25122 C dec efiicient contacting of the mixture of oxidizing 114F223: (P2023 1203: Pyroghosghoricsl 61 C. gases P hydmFarbon Vap9rs undergolng treat?- neroi (P205.3Hz0).. Orthophosphoric--. M. P. 3s.c 0.; ment, with the liquid or solid acids and the solid contact masses may be employed. The contact materials may sometimes be employed in succes- 35 We have found that the different acids of sive strata of varying composition or supported P sphorus may be adva ta us y ployed i on superimposed trays designed to produce intithe treatment of hydrocarbon oil vapors, parmate ontact. ti ula lv those m d from t ra of r a- It has been found desirable to neutranze the tlvely heavy hydroqal'bon Oil miXtureS- Will vapors before or after condensation and to this 40 be seen if Om a consldemtion 0f the table of end the vapors may be treated with ammonia gas p t of the acids 0f phosphorus that the nature or pass counterflow to solutions of alkalies in of .the treating effect may be varied over a conauxiliary neutralizing equipment r t siderable range by utilizing acids of different densed vapors may be t t t liquid alkap p y Using acids Containing highly oxilies such as solutions of caustic soda, ammonia 45 diZed anhydrides of phosphorus and Substantial or the like, the traces of reagents and reaction p p s of oxidizing gases mixed With Oil products remaining being washed out with water vapors, distinct polymerizing effects may be pro when found necessary. duced, these effects extending in many instances The amounts of reagents used in t t t to reactior} SuIfuF'POmaminE m comprised within the sc ope of the invention will 50 bQnS- Wlth aclds contammg less mgmy vary with the character of the vapors treated, the iz d Ph in other Words, the Oxides temperatures and pressures employed and other of Phosphorus Of a lower Valeme, the treating factors. Amounts of phosphorus acids may be effect may be moderated so that controllable employed from a fraction of a percent by weight amounts of unsaturated compou s may be reof oil treated to as high as 10% or higher in cases produced from California oils.

Various temperatures of treatment may be employed, for example, from 250600 F., more or less, and the pressuresmay be subatmospheric, atmospheric, or superatmospheric. While the results may vary with the conditions employed, the pressures and temperatures are chosen so that the hydrocarbons are treated substantially in the vapor phase.

As specific examples of the operation of the process of theiinvention and of the results obtained, a California cracked distillate of approximatelymotor fuel boiling range may be vaporized and subjected to treatment with orthophosphoric acid (see table) of approximately concentration, the vapors being mixed with small amounts of air or oxygen and steam during their passage in a downward direction through, a stationary mass of fullers earth. The phosphoric acid may be used in an amount equivalent to approximately six pounds per barrel. Steam is used at the rate of approximately two pounds per barrel. The untreated product may show a gum content of approximately 500 mgs. per ccs. and have a reddish-brown color, with a sulfur content of approximately 0.45%. The treated product after suitable separation from spent reagents, neutralizing with alkalies and washing with water may show a gum content of approximately 18 mgs. and a color of plus 30 on the Saybolt scale. The sulfur content may be found to be as low as 0.1%. g

In the case of a mixed Mid-Continent and West Texascracked distillate treated with approximately the same amounts of reagents, the gum content may be reduced from 300 mgs. to 10 andthe color raised from a light amber to ap-- proximately 30 on the Saybolt scale. The sulfur content may be reduced from 0.4% to 0.2% approximately.

Theprocess of the invention is particularly suitable to the treatment of cracked distillates In some cases the untreated distillates may contain 700 mgs. of

gum and have a dark reddish color, while the treated distillates may have a gum content of only 60 mgs. and a color of 25 to 30 on the Saybolt scale. The sulfur content may be reduced from 0.4% to 0.1%.

The foregoing description and examples have disclosed a process applicable to the treatment of hydrocarbon oil vapors which has a wide applicability and is capable of great variations in the methods of operation and the amounts of reagents employed. Therefore, the specific cases cited are not to be construed in a limiting sense upon the broad scope of the invention, as many other modifications and examples can be given.

We claim as our invention:

1. A step in the refining of the overhead products resulting from the cracking of hydrocarbon oil, which comprises subjecting said products in heated vaporous condition to the action of an acid of phosphorus and a free oxygen containing gas in the presence of a non-metallic solid contacting agent.

2. A step in the refiningof the overhead products resulting from the cracking of hydrocarbon oil, which comprises subjecting said products in heated vaporous condition to the ,action of an acid of phosphorus and a free oxygen containing gas in the presence of bauxite.

3. A step in the refining of the overhead products resulting from the cracking of hydrocarbon oil, which comprises subjecting said products in heated vaporous condition to the action of an acid of phosphorus and a free oxygencontaining gas in the presence of fullers earth.

4. A step in the refining of the overhead products resulting from the cracking of hydrocarbon oil, which comprises subjecting said products in heated vaporous condition to the action of an acid of phosphorus and a free oxygen containing gas in the presence of a zeolite.

JACQUE C. MORRELL. GUSTAV EGLOFF. 

